Novel o,o-dialkyl-o-(carboxy-alkenyl)-phosphoric acid compounds



- United States Patent US. Cl. 260942 6 Claims ABSTRACT OF THEDISCLOSURE The compounds are novel derivatives of 0,0-dialkylO-(carboxy-alkenyl)-phosphoric acid useful as insecticidal andacaricidal agents with low toxicity toward warmblooded animals and lowvolatility.

This invention relates to novel0,0-dialkyl-O-(carboxyalkenyl)-phosphoric acid compounds as well as to aprocess of preparing such compounds.

More particularly, the present invention concerns a novel class ofphosphoric acid derivatives of the formula wherein R and R which may beidentical to or different from each other, are alkyl of 1 to 4 carbonatoms, R is hydrogen, chlorine or bromine, R is hydrogen or methyl, R iscyano, COOR or where R; is alkyl of 1 to 6 carbon atoms, and R and Rwhich may be identical to or different from each other, are hydrogen,straight or branched alkyl of 1 to 6 carbon atoms, cycloalkyl of up to 6carbon atoms, aryl or aralkyl or, together with each other and thenitrogen atom to which they are attached, form a basic heterocyclicring, such as morpholino or pi-peridino, and R is hydrogen or, if R iscyano, lower alkyl.

The compounds according to the present invention may be prepared by aprocess which involves well known chemical principles, that is, byreacting an acetoacetylhydroxy carboxylic acid derivative of the FormulaII with a trialkyl phosphite of the Formula III at elevatedtemperatures, pursuant to the following reaction equation:

- wherein X is chlorine or bromine and R through R have the samemeanings as in Formula I. If R, and R are alkyl of a different number ofcarbon atoms, then R, designates the one with a lesser number of carbonatoms.

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The reaction between compounds II and III may be carried out with orwithout a solvent medium. In the event that no solvent is used, thereaction often begins already at room temperature after the reactantshave been admixed with each other, which is evidenced by a clearlynoticeable increase in the internal temperature of the reaction mixture,and is brought to completion by heating the mixture, preferably to -1 20C.

If the reaction is carried out in the presence of a solvent, it ispreferred to use an inert organic solvent such as benzene, toluene,xylene, chlorobenzene or dioxane, chlorobenzene being particularlypreferred. Under these conditions the reaction mixture is held for oneto three hours at preferably 80l20 C., and the trialkyl phosphite III isprovided in an amount slightly in excess of the amountstoichiometrically required for reaction with starting compound II. Theprogress of the reaction may be followed by condensing and Weighing thealkyl halide R X formed by the reaction; in general, it goes tocompletion after one to three hours. Thereafter, the solvent and theexcess unreacted trialkyl phosphite are removed by vacuum distillation,and the reaction product remains as a colorless to reddish-brown oilyresidue.

Those raw reaction products of the Formula I wherein R is cyano or-COOR- may be purified by fractional vacuum distillation. The rawreaction products of the Formula I wherein R is -CONR R arewater-soluble and may be adequately purified by dissolving them inwater, treating the solution with activated charcoal, and extracting thepurified product with methylenechloride. They cannot be distilledwithout decomposition at 0.1 mm. Hg.

A starting compound of the Formula II may be obtained by reacting ahydroxy-carboxylic acid of the formula R0 (IV) wherein R R and R havethe same meanings as in Formula I, with diketene, or by double esterdecomposition of methyl or ethyl acetate with an amide or nitrile of theFormula IV, followed by chlorination or bromination. The chlorinationmay readily be accomplished with one or two molar equivalents ofsulfuryl chloride.

The following examples further illustrate the instant invention and willenable others skilled in the art to understand it more completely. Itshould be understood, however, that the invention is not limited solelyto the particular examples given below.

EXAMPLE 1 Preparation of0,0-dimethyl-O-[1-(ethoxycarbonylmethoxycarbonyl)-1-propen-2-yl]-phosphate 22.3 gm. (0.1 mol) of2-chloroacetoacetyl-glycolic acid ethylester were added dropwise, whilestirring, to a boiling solution of 14.9 gm. (0.12 mol) oftrimethylphosphite in 30 cc. of chlorobenzene in a three-neck flaskprovided with a stirrer, dropping funnel and reflux cooler, the latter,in turn, being connected to a cooled condenser trap. Thereafter, thereaction solution was refluxed for another hour. At the end of this time3.5 gm. of methyl chloride had collected (calculated amount: 5.05 gm.; aportion remained in the apparatus). The chlorobenzene and the excessunreacted trimethyl phosphite were then distilled off in vacuo on aboiling water bath. 27.8 gm. of a yellow oil remained behind, which werepurified by vacuum distillation. 23.6 gm. (79.5% of theory) of acolorless liquid, B.P. 142-143 C. at 0.01 mm. Hg, were obtained. It wasidentified to be 0,0-dimethyl-O- 1- (ethoxycarbonylmethoxycarbonyl)-1-penten- 2-yl1-phosphate of the formula CHaO O 01130 (3=CHCO O CHz-C OO C2115 Analysis (mol. Wt. 296.2).Calculated: P, 10.48%. Found: P,10.50%.

EXAMPLE 2 Using a procedure analogous to that described in Example 1,0,0-dimethyl-O-[l-(ethoxycarbonyl-ethoxycarbonyl)-1-propen-2-yl]-phosphate,B.P. 138-l40 C. at 0.005 mm. Hg, of the formula CH3 CH3 was preparedfrom trimcthylyphosphite and 2-chloroacetoacetyl-lactic acid ethylester. The yield was 86% of theory.

EXAMPLE 3 Using a procedure analogous to that described in Example 1,0,0-diethyl-O[1-methoXycarbonyl-ethoxycarbonyl)-1-propen-2-yl]-phosphate,B.P. 145152 C. at 0.2 mm. Hg, of the formula CH3 CH3 was prepared fromtrimethylphosphite and 2-chloroacetoacetyl-lactic acid mehtyl ester. Theyield was 94.4 of theory.

EXAMPLE 4 Using a procedure analogous to that described in Example 1,0,0-dimethyl-O-[1-methoXycarbonyl-eth0xycarbonyl)-2-propen-2-yl-phosphate,B.P. 140 C. at 0.01 mm. Hg, of the formula CH3 CH3 was prepared fromtriethylphosphite and 2-chloroacetoacetyl-lactic acid methyl ester. Theyield was 77.2% of theory.

EXAMPLE 5 Using a procedure analogous to that described in Example 1,0,0-dimethyl O [l (ethoxycarbonylmethoxycarbonyl)-1-chloro-1-propen-2-yl] phosphate, B.P. 160-162 C. at0.01 mm. Hg, of the formula was prepared from trimethylphosphite and2,2-dichloroacetoacetyl-glycolic acid ethyl ester. The yield was 85.5%of theory.

EXAMPLE 6 Using a procedure analogous to that described in Example 1,0,0 diethyl O [1-(ethoxycarbonyl-ethoxy- 4carbonyl)-1-propen-2-yl]-phosphate, B.P. 142-145 C. at 0.01 mm. Hg, ofthe formula CzHrO O CH3 CH3 was prepared from triethylphosphite and2-chloroacetoacetyl-lactic acid ethyl ester. The yield was 80.5% oftheory.

EXAMPLE 7 Using a procedure analogous to that described in Example l,0,0-dimethyl-O-[1-(methoxycarbonyl-ethoxycarbonyl)-1-chloro-1-propen-2-yl]-phosphate,B.P. 158- 160 C. at 0.03 mm. Hg, of the formula CH3 CH3 was preparedfrom trimethylphosphite and 2,2-dichloroacetoacetyl-lactic acid methylester. The yield was 88.5% of theory.

EXAMPLE 8 Using a procedure analogous to that described in Example 1,0,0-diethyl-O [1-(methoxycarbonyl-ethoxycarbonyl) lchloro-l-propen-Zyl]-phosphate, B.P. C. at 0.02 mm. Hg, of the formulawas prepared from trimethylphosphite and 2-chloroacetoacetyl-glycolicacid n-butyl ester. The yield was 90.4% of theory.

EXAMPLE 10 Using a procedure analogous to that described in Example 1,0,0-diethyl-O[1-(n-butoxycarbonyl-methoxycarbonyl)-1-propen-2-yl]-phosphate, B.P.163166 C. at 0.005 mm. Hg, of the formula was prepared fromtriethylphosphite and 2-chloroacetoacetyl--glycolic acid n-butyl ester.The yield was 87.2% of theory.

EXAMPLE 11 Preparation of 0,0-dimethyl-O [l-(n-butoxycarbonylmethoxycarbonyl) l-chloro 1-propen-2-yl]-phosphate without solvent medium 14.8gm. (0.12 mol) of trimethylphosphite were added dropwise over a periodof 15 minutes to 28.5 gm. (0.1 mol) of 2,2-dichloroacetoacetyl-glycolicacid n-butyl ester (B.P. 116-1l7 C. at 0.03 mm. Hg), accompanied bystirring, whereby he internal temperature of the reaction mixture roseto 40 C. After all of the trimethyl phosphite had been added, thereaction mixture was stirred for one and a half hours at 90 C. on awater bath. Thereafter, the excess unreacted trimethyl phosphite wasdistilled off in vacuo, leaving 34.5 gm. of a yellow oil as a residue,which was purified by fractional vacuum distillation. The fractionpassing over between 165 and 168 C. at 0.15 mm. Hg was collected. 27 gm.(75% of theory) of a colorless viscous liquid was obtained, which wasidentified to be 0,0-dimethyl-O [l-(butoxycarbonylmethoxycarbonyl)-l-chloro-propen-2-yl] -phosphate, mol. wt. 358.7, of the formula CHsO Oacetoacetyl lactic acid isopropyl ester. The yield was 93.7% of theory.

EXAMPLE 13 Using a procedure analogous to that described in Example 11,0,0-diethyl-O-[1-(isopropoxycarbonyl-ethoxycarbonyl)-l-propen-2-yl]-phosphate,B.P. 158-161 C. at 0.3-0.7 mm. Hg, of the formula was prepared fromtriethyl phosphite and 2-chloroacetoof theory.

EXAMPLE 14 Using a procedure analogous to that described in Example 11,0,0-dimethyl-O [1-(ethoxycarbonyl-ethoxycarbonyl-l-bromo-Lpropen-Z-yl]phosphate, B.P. 151 164 C. at 0.05 mm. Hg (decomposition), of theformula was prepared from trimethyl phosphite and2,2-dibromoacetoacetyl-lactic acid ethyl ester. The yield was 61.5%

of theory.

EXAMPLE 15 Using a procedure analogous to that described in Example 11,0,0-diethyl-O [1(ethoxycarbonyl-ethoxycarbonyl)l-bromo-l-propen-Z-yl]-phosphate of theformula CzHaO 6 Was prepared from triethyl phosphite and2,2-dibromoacetoacetyl-lactice acid ethyl ester. The yield of rawproduct was 97.5% of theory.

EXAMPLE 16 Using a procedure analogous to that described in Example 11,except that a vacuum of about mm. Hg was maintained throughout thereaction period, 0,0-din-butyl O [l(methoxycanbonyl-ethoxycarbonyl)-lpropen-Z-yl]phosphate, B.P. l48l50 C.at 0.01 mm. Hg, of the formula was prepared from tri-n-butyl phosphiteand 2-chloroacetoacetyl-lactic acid methyl ester. The yield was 67.2% oftheory.

EXAMPLE 17 Using a procedure analogous to that described in Example l1,0.0-diisopropyl O [l (methoxycarbonybethoxy-carbonyl)-l-propen-2-yl]-phosphate, B.P. 137- 152 C., of theformula CH CH2 was prepared from triisopropyl phosphite and2-chloroacetoacetyl-lactic acid methyl ester. The yield was 53.2% oftheory.

EXAMPLE 18 Preparation of 0,0-dimethyl-O-ll-dimethylcarbamylethoxy-carbonyl) -1-propen-2-yl] -phosphate 23.5 gm.(0.1 mol) of 2-chloroacetoacetyl-lactic acid dimethylamide were admixedwith 16.1 gm. (0.13 mol) of trimethyl phosphite in a three-neck flaskprovided with a stirrer, thermometer and reflux cooler, the latter beingin turn connected to a cooled condenser trap. The temperature of themixture rose to about 40 C. The mixture was then stirred for two hourson a boiling water 'bath. At the end of this time 3 gm. ofmethylchloride had collected in the trap. The contents of the reactionflask were then charged into a rotary evaporator and allowed to remaintherein for thirty minutes at C. under a vacuum of 0.1 mm. Hg in orderto remove the unreacted trimethyl phosphite. The residual brown oil wastaken up in 200 cc. of water, and the cloudy solution was shaken withgasoline and then treated with activated charcoal. The gasoline phasewas discarded, and the clear aqueous phase was extracted several timeswith methylene chloride. The combined methylene chloride extractsolutions were dried over sodium sulfate and then evaporated. 2 7 gm.(87.2% of theory) of a yellow oil were obtained, which was identified tobe0,0-dimethyl-O-[l-(l-dimethylcarbamylethoxycarbonyl)-1-propen-2-yl]phosphateof the formula orno o CH CH3 Analysis (mol. wt. 309.2); n=1.4770.-Calculated: N, 4.51%; P, 10.0%. Found: N, 4.59%; P, 9.85%.

When a sample of the product was subjected to distillation at 0.1 mm.Hg, it underwent partial decomposition.

EXAMPLE 19 Using a procedure analogous to that described in Example 18,0,0-diethyl-O-[1-(dimethylcarbamyl-ethoxy- 7 carbonyl)-1-propen-2-yl]-phosphate, a light brown oil, n =1.4720, of the formula C2H5O O \PC2H5O/ OIC=CHCOOCEOON(CHB)Z CH3 OH: was prepared from triethyl phosphiteand 2-chloroacetoacetyl-lactic acid dimethylamide. The yield was 71.8%.Analysis.Calculated: N, 4.17%. Found: N, 4.33%.

EXAMPLE 20 Using a procedure analogous to that described in EX- ample18, 0,0-dimethyl-O-[l-(methylcarbamyl-ethoxycarbonyl)-1-propen-2-y1]-phosphate, a yellow viscous oil, n =1.4763, of the formula OHsO O wasprepared from triethyl phosphite and 2-chloroacetoacetyl-lactic acidmethylamide. The yield was 76.2% of theory.

Analysis.Calculated: N, 4.33%. Found: N, 4.40%.

EXAMPLE 22 Using a procedure analogous to that described in Example 18,0,0 dimethyl-O-[l-(l-dimethylcarbamylethoxy-carbonyl-l-chloro 1propen-2-yl1-phosphate, a brown oil of the formula CH30\ O P CHaO wasprepared from trimethyl phosphite and 2,2-dichloroacetoacetyl-lacticacid dimethylamide. The yield was 77.2% of theory.

Analysis.- Calculated: N, 4.08%. Found: N, 3.94%.

'EXAMPLE 23 Using a procedure analogous to that described in Example 18,0,0-diethyl-O-[1-(l-dimethylcarbamyl-ethoxycarbonyl) 1chloro-l-propen-Z-yl]-phosphate, a dark brown oil of the formula wasprepared from triethyl phosphite and 2,2-dichloroacetoacetyl-lactic aciddimethylamide. The yield was 96% of theory.

Analysis.-Calculated: N, 3.76%. Found: N,3.19%.

8 EXAMPLE 24 Using a procedure analogous to that described in Example18,0,0-dimethyl-O-[l-(ethylcarbamyl-methoxycarbonyl)-1-propen-2-yl]-phosphate,a brown oil of the formula CHsO O omo 0(]3=CH--COOCHzCONHCzHs CH3 wasprepared from trimethyl phosphite and 2-chloroacetoacetyl-glycolic acidethylamide. The yield was 96.5% of theory.

An-alysis.-Calculated: N, 4.75%. Found: N, 4.56%.

EXAMPLE 25 Using a procedure analogous to that described in Example 18,0,0-dimethyl-O- 1-(ethylcarbamyl-methoxycarbonyl)-1-chloro-1-propen-2-yl]-phosphate, abrown oil of the formula \OC=GC1COOCH2-CONHC2H5 CH3 was prepared fromtrimethyl phosphite and 2,2-dichloroacetoacetyl-glycolic acidethylamide. The yield was 84.5% of theory.

Analysisx Calculatedz N, 4.25%. Found: N, 4.06%.

EXAMPLE 26 Using a procedure analogous to that described in Example 18,0,0-diethyl-O-[1-(ethylcarbamyl-methoxycarbonyl)-1-propen-2-yl]-phosphate,a brown oil of the formula CHaO was prepared from triethyl phosphite and2-chloroacetoacetyl-glycolic acid ethylamide. The yield was 88% oftheory.

Analysis.Calculated: N, 4.33%. Found: N, 4.10%.

EXAMPLE 27 Using a procedure analogous to that described in Example 18,0,0-diethyl-O-[1-(ethylcarbamyl-methoxycarbonyl)-1-chloro-l-propen-2-yl]-phosphate,a brown oil of the formula was prepared from triethyl phosphite and2,2-dichloroacetoacetyl-glycolic acid ethylamide. The yield was 92% oftheory.

Analysis.Calculated: -N, 3.92%. Found: N, 3.62%.

EXAMPLE 28 Using a procedure analogous to that described in Example 18,0,0-dimethyl-0- 1-( l-morpholinocarbonylethoxycarbonyl)-1-propen-2-yl]-phosphate, a yellow oil, n =1.4859, of the formulawas prepared from trimethyl phosphite and 2-chloroacetoacetyl-lacticacid morpholide. The yield was 82% of theory.

Analysis.Calculated: N, 3.98%. Found: N, 3.50%.

EXAMPLE 29 Using a procedure analogous to that described in Example 18,0,0-diethyl O[l-(l-morpholinocarbonylcthoxycarbonyl)-l-propen-2-yl]-phosphate, ayellow oil, n =1.4748, of the formula CZIISO o \O(|?=CHCOCHC0N/ o CH3CH3 g was prepared from triethyl phosphite and 2-chloroacetoacetyllacticacid morpholide. The yield was 73% of theory.

Analysis.-Calculated: N, 3.69%. Found: N, 3.40%.

EXAMPLE 30 Using a procedure analogous to that described in Example 18,0,0-dimethyl-O-[1-(diethylcarbamyl-methoxycarbonyl)-1-propen-2-yl]-phosphate,a dark red oil, n =1.4781, of the formula CHaO O was prepared fromtrimethyl phosphite and 2-chloroacetoacetyl-glycolic acid diethylamide.The yield was 70% of theory.

Analysis-Calculated: N, 4.33%. Found: N, 4.33%.

EXAMPLE 31 Using a procedure analogous to that described in EX- ample18,0,0-diethyl-O-[1-(diethylcarbamyl-methoxycarbonyl)-l-propen-2-yl]-ph0sphate,a dark red oil, n =1.4722, of the formula was prepared from triethylphosphite and 2-chloroacetoacetyl-glycolic acid diethylamide. The yieldwas 57% of theory.

Analysis.Calculated: N, 3.99%. Found: N, 3.90%.

EXAMPLE 32 Using a procedure analogous to that described in Example 18,0,0-dimethyl-O-[ 1-( l-morpholinocarbonylethoxycarbonyl)-1-chloro-1-propen-2-yl]-phosphate, a red oil, n =1.4888, ofthe formula CH3 CH3 CHaO was prepared from trimethyl phosphite and2,2-dichloroacetoacetyl-lactic acid morpholide. The yield was 64% oftheory.

Analysis.-Calculated: N, 3.64%. Found: N, 3.15%.

EXAMPLE 33 Using a procedure analogous to that described in Example 18,0,0-dimethy1-O-[1-(l-morpholinocarbonyl- 10 ethoxycarbonyl)-1-chloro-1-propen'2-yl]phosphate, a dark red oil of theformula CzHsO O \OCIT=CCICOOCHCON \O CH CH3 was prepared from triethylphosphite and 2,2-dichloroacetoacetyl-lactic acid morpholide. The yieldwas 94% of theory.

Analysis.Calculated: N, 3.36%. Found: N, 2.98%.

EXAMPLE 34 Using a procedure analogous to that described in Example 18,0,0 dimethyl O [l(dimethylcarbamylmethoxy-carbonyl)-1-propen-2-yl]-phosphate, a dark redoil, n =1.4748, of the formula CHsO was prepared from trimethylphosphite and 2-chlorOacetoacetyl-glycolic acid dimethylamide. The yieldwas 64% of theory.

Analysis.Calculated: N, 4.77%. Found: N, 4.80%.

EXAMPLE 35 Using a procedure analogous to that described in EX- ample18,0,0-diethyl-O-[1-(dimethylcarbamyl-methoxycarbonyl)-1-propen-2-yl]-phosphate,a dark red oil, n =1.4700, of the formula was prepared from triethylphosphite and 2-chloroacetoacetyl-glycolic acid dimethylamide. The yieldwas 71% of theory.

Analysis.-Calculated: N, 4.35%. Found: N, 4.27%.

theory.

Analysis.Calculated: N, 4.63%. Found: N, 4.39%.

EXAMPLE 37 Using a procedure analogous to that described in Example 18,0,0-dimethyl-O-[1-(methylcarbamyl-methoxycarbonyl) 1chloro-l-propen-Z-yl]-phosphate, a dark brown oil of the formula wasprepared from trimethyl phosphite and 2,2-dichloroacetoacetyl-lacticacid methylamide. The yield was 70% of theory. 1

Analysis.-Calculated: N, 4.47%. Found: N, 4.50%.

1 1 EXAMPLE 38 Using a procedure analogous to that described in Example18,0,0-diethy1-0-[l-(methylcarbamyl-methoxycarbonyl)-l-chloro-l-propen-2-yl]-phosphate,a dark oil of the formula was prepared from triethyl phosphite and2,2-dichlorc acetoacetyl-glycolic acid methylamide. The yield was 83% oftheory.

Analysis.Calculated: N, 4.07%. Found: N, 4.05%.

was prepared from trimethyl phosphite and 2-chloroacetoacetyl-glycolicacid phenylamide. The yield was 53% of theory.

Analysis.-Calculated: N, 4.08%; P, 9.04%. Found: N, 4.56%; P, 8.91%.

EXAMPLE 40 Using a procedure analogous to that described in Example 18,0,0-diethyl-O-[l-(phenylcarbamyl-methoxycarbonyl) 1chloro-l-propen-Z-yl]-phosphate, a light brown oil, n =1.5051, of theformula was prepared from triethyl phosphite and 2,2-dichloroaacetoacetyl-glycolic acid phenylamide. The yield was 93% of theory.

Analysis.--Calculated: N, 3.45%; Cl, 8.76%. Found: N, 3.18%; Cl, 8.10%

EXAMPLE 41 Preparation of 0,0-dimethyl-O- 1-(ethylcarbamylethoxycarbonyl) -1-propen-2-yl] -phosphate 23.5 gm. (0.1mol) of a-chloroacetoacetyl-lactic acid ethylamide were dissolved in 50cc. of chlorobenzene, the solution was admixed with 16.1 gm, (0.13 mol)of trimethyl phosphite, and the mixture was stirred for three hours at120 C. Thereafter, the reaction solution was evaporated in vacuo, theresidue (30 gm.) was taken up in 200 cc. of water, and the solution wasextracted with cc. of petroleum ether. The petroleum ether extractsolution was discarded, and the aqueous phase was treated with activatedcharcoal. The aqueous phase was then extracted several times withmethylene chloride, the extract solutions were combined, and thecombined solution was dried and evaporated. 19 gm. (61.4% of theory) ofa yellow oil were obtained, which solidified upon prolonged standing atroom temperature. It was identified to be 12 0,0 dimethyl O[1-(ethylcarbamylethoxycarbonyl)- 1-propen-2-yl1-phosphate of theformula 1 omo o-o=oH-oo0( HooNHo2H5 CHa CH3 Analysis (mol. wt.309.2).Calculated: N, 4.51%; P, 10.0%. Found: N, 4.65%; P, 9.8%.

EXAMPLE 42 Using a procedure analogous to that described in Example 41,0,0 diethyl O-[1-(ethylcarbamyl-ethoxycarbonyl) 1 propen 2 yl]-phosphate, a light yellow oil, n =1.4504, of the formula C2H5O O wasprepared from triethyl phosphite and u-chloroacetm acetyl-lactic acidethylamide, The yield was 88.7% of theory.

Analysis.Calculated: N, 4.15%. Found: 'N, 3.80%.

EXAMPLE 43 Using a. procedure analogous to that described in Example 41,0,0-dimethy1-O-[l-(ethylcarbamyl-ethoxycarbonyl) 1chlorO-l-propen-Z-yl]-phosphate, a brown oil, n =1.4683, of the formula(EH30 o-o=oo1o0o( 1H-CONHOzHi CH3 C 3 was prepared from trimethylphosphite and a,a-dichloroacetoacetyl-lactic acid ethylamide, The yieldwas 86.5% of theory.

Analysis.Calculated: N, 4.08%. Found: N, 4.02%.

EXAMPLE 44 Using a procedure analogous to that described in Example 41,0,0 diethyl O-[1-(ethylcarbamyl-ethoxycarbonyl) 1chloro-l-propen-Z-yl]-phosphate, a reddishbrown oil, n -=I.4S9S, of theformula 021150 O(J=CC1COOCHCONECzHs CH3 CH3 was prepared from triethylphosphite and 0:,a-di6hl010- acetoacetyl-lactic-acid ethylamide. Theyield was 94.4% of theory.

Analysis.Calculated: N, 3.77%. Found: N, 3.41%.

EXAMPLE 45 Using a procedure analogous to that described in Example 41,0,0-dimethy1-O-[1-(piperidinocarbonyl-ethoxycarbonyl)-l-propen-2-yl]-phosphate, a light brown oil, n =1.4887, of the formula was preparedfrom trimethyl phosphite and a-ChlOIO- acetoacetyl-lactic acidpiperidide. The yield was 90.3% of theory.

Analysis.-Calculated: N, 4.01%. Found: N, 4.05

EXAMPLE 46 Using a procedure analogous to that described in Example 41,0,0-dimethyl-O-[1-(isopropylcarbamyl-ethoxy- CH3 2113 H was preparedfrom trimethyl phosphite and a-chloroacetoacetyl-lactic acidisopropylamide. The yield was 92.1% of theory.

Analysis.Calculated: N, 4.33%. Found: N, 4.23%.

EXAMPLE 47 Using a procedure analogous to that described in Example 41,0,0-dimethyl-O-[ 1-(methylcarbamyl-methoxycarbonyl)-1-propen-2-yl]-phosphate, a brown oil,

n =1.4752 of the formula c1130 O(IJ=CHCOOOH2CONHCHa was prepared fromtrimethyl phosphite and a-chloroacetoacetyl-glycolic acid methylamide.The yield was 62% of theory.

AnaIysis.-Calculated: N, 4.97%. Found: N, 4.75%.

EXAMPLE 48 Using a procedure analogous to that described in Example 41,0,0-dimethyl-O-[l-(morpholinocarbonyl-ethoxycarbonyl)-1-propen-2-yl]-phosphate,a yellow oil,

n -=1.4951 of the formula onto 0 CHaO \OC=CH-COOCH-CON o CH CH3 wasprepared from trimethyl phosphite and u-chloroacetoacetyl-latic acidmorpholide. The yield was 95% of theory.

AnaIysis.-Calculated: N, 4.56%. Found: N, 4.45%.

EXAMPLE 49 Preparation of 0,0-dimethyl-O-[ ll-cyano ethoxycarbonyl)-(l-propen-2-yl1-ph0sphate 22.8 gm. (0.12 mol) ofu-chloroacetoacetyl-lactic acidnitrile were added dropwise, whilestirring, to a boiling solution of 18.0 gm. (0.145 mol) of trimethylphosphite in 75 cc. of chlorobenzene in a three-neck flask provided witha stirrer, dropping funnel and a reflux cooler, the latter in turn beingconnected to a cooled condenser trap. Altogether, the reaction solutionwas maintained at the reflux temperature for two hours. At the end ofthat time 6.0 gm. (calculated 6.6 gm.) of methyl chloride had collectedin the trap. The reaction solution was then evaporated, and the residuewas distilled in vacuo. The yellow liquid passing over between 138 and140 C. at 0.04 mm. Hg was identified to be 0,0-dimethyl-O-[l-(l-cyano-ethoxycarbonyl)-l-propen-2-yl]-phosphate of the formula P CHaOO-C=CHCOOCH-CN JHa CH3 EXAMPLE 50 Using a procedure analogous to thatdescribed in Example 49, 0,0-diethyl-O-[l (1 cyano-ethoxycar- 14bonyl)-l-propen-2-yl]-phosphate, B.P. 134-136 C. at 0.01 mm. Hg, of theformula was prepared from triethyl phosphite and a-chlor0acetoacetyl-lactic acid-nitrile. The yield was 71.5% of theory.

EXAMPLE 51 Using a procedure analogous to that described in Example 49,0,0-diethyl-O- l-(cyano-methoxycarbonyl 1-propen-2-yl]-phosphate, B.P.C. at 0.02 mm. Hg, of the formula CHa was prepared from triethylphosphite and a-chloroacetoacetyl-glycolic acid-nitrile. The yield was80.4% of theory.

EXAMPLE 52 Using a procedure analogous to that described in Example 49,0,0-dimethyl-O [l (cyano-isopropoxycarbonyl)-1-propen-2-yl]-phosphate,B.P. 149-152 C. at 0.05 mm. Hg, of the formula was prepared fromtrimethyl phosphite and a-ChlOlO- acetoacetyl-isobutyronitrile. Theyield was 77.8% of theory.

The compounds according to the present invention, that is, thoseembraced by Formula I above, have useful properties. More particularly,they exhibit highly effective insecticidal and acaricidal properties,coupled with low toxicity toward warm-blooded animals and lowvolatility. The compounds are particularly effective against Aphisfabae, Doralis fabae, Metatetranychus ulmi and T etraanychus urticae.

For insecticidal and acaricidal purposes the compounds of the instantinvention are disseminated in customary fashion, that is, by spraying,dusting, brushing or the like, so that the insects and acarids intendedto be killed come in direct contact with the compounds. The compoundsmay be used as such for this purpose or in admixture with inert gaseous,liquid or solid carriers. Examples of compositions consisting of one ormore of the compounds according to the invention in admixture with aninert carrier are dusting powders, suspensions, emulsions, solutions,aerosols and the like. Such compositions may, in addition, contain otherinsecticidal and acaricidal agents as Well as auxiliary components, suchas emulsifiers, wetting agents and additives which enhance the abilityof the composition to adhere to solid surfaces. The effective range ofconcentration of the compounds according to the invention incompositions of the type referred to above is between about 0.005 andabout 5% by weight, based on the total weight of the composition.

The following examples illustrate a few insecticidal and acaricidalcompositions comprising a compound of the instant invention as an activeingredient. The parts are parts by weight.

15 EXAMPLE 53 Emulsion 40 parts of0,0-dimethyl-O-[l-(l-ethoxycarbonylethoxycarbonyl)-1-propen-2-yl]-phosph ate were admixed with 20 parts of xylene and Y40 parts ofnaphthalene sulfonate, and the mixture was emulsified in a sufficientamount of water to make the concentration of the phosphate compound inthe finished emulsion from 0.01 to 0.2% by weight. The resulting aqueousemulsion was a highly effective insecticidal and acaricidal compositionparticularly adapted for dissemination by spraying.

EXAMPLE 4 Suspension 25 parts of0,0-dimethyl-O-[l-(l-methoxycarbonylethoxycarbonyl)-1-propen-2-yl]-phosphatewere admixed with five parts of naphthalene sulfonate and 20 parts ofkaolin, the mixture was milled, and the resulting wettable powder wassuspended in a sufiicient amount of water to make the concentration ofthe phosphate compound in the aqueous suspension from 0.01 to 0.2% byweight. The suspension was a highly effective insecticidal andacaricidal composition particularly adapted for dissemination byspraying or brushing.

EXAMPLE 55 Dusting powder 2 parts of 0,0-diethyl-O-[l (1methoxycarbonylethoxycarbonyl)-1-propen-2-yl] -phosphate were admixedwith 98 parts of kaolin, and the mixture was milled into a homogeneouspowder. The powder was a highly efiective insecticidal and acaricidalcomposition.

EXAMPLE 5 6 Aerosol spray We claim: 1. A compound of the formula R3 I H1320 \OC=(JCOO-CHCOOR1 wherein R and R are each alkyl of 1 to 4 carbonatoms, R is hydrogen, chlorine or bromine, R is hydrogen or methyl, andR is alkyl of 1 to 6 carbon atoms. 2. A compound of the formula whereinR and R are methyl or ethyl,

R is hydrogen, chlorine or bromine,

R is hydrogen or methyl, and

R is alkyl of 1 to 4 carbon atoms.

3. A compound according to claim 1, wherein R and R are methyl, R ishydrogen, R is methyl and R7 is ethyl.

4. A compound according to claim 1, wherein R R R and R are methyl and Ris hydrogen.

5. A compound according to claim 1, wherein R and R and R are ethyl, Ris hydrogen and R and R are methyl.

6. A compound according to claim 1, wherein R R and R are methyl, R ishydrogen and R is isopropyl.

References Cited UNITED STATES PATENTS 3,196,190 7/1965 Nischk et al260-942 FOREIGN PATENTS 867,780 5/ 1961 Great Britain.

ALEX MAZEL, Primary Examiner J. H. TURNIPSEED', Assistant Examiner US.Cl. X.R.

mgr UI'IITEDI STATES PATENT OFIIPICE CERTIFICATE OF CORRECTION lfatentNo. 6 6,7 8 Dated F 97 "io1fpn5 Buck, Richard Behring and Karl Zeile It1 certified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

7001. 3, line 22: gter "94A" insert 1 lino -propcn" should read--l-propen--;

insert after "yl".

001. 5, line 47: before "of theory" insert --eoety1-1actic I acidiaopropyl eater. mo yield was 94.6%.

I 001. 7, line 32: asso" should read "1.4680" 001. 8, fix-at formula:"8" should read --P--.

001. 9, line 75: "dimethyl" should read "methyl".

Col 16, line 30: delete "R and".

Signed and sealed this 1st day of September 1970.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. 4 WILLIAM E. SCHUYLER, JR. Attestip-g OfficerCommissioner of Patents

